Method for inhibiting plant growth with quaternary ammonium salts

ABSTRACT

WHEREIN A is a lower alkylene, a lower alkenylene or a lower alkadienylene; R1 and R2 are each lower alkyl which may be linked together directly or by an oxygen atom to form a saturated heterocyclic group; R3 is a lower alkyl, a halo(lower)alkyl, a lower alkynyl, a phenyl(lower)alkyl which may have one or more halogen atoms as substituents on the phenyl ring, a lower alkenyl, a hydroxy(lower)alkyl, a carboxy(lower)alkyl or a lower alkenyloxycarbonyl(lower)-alkyl; R4, and R5 and R6 are each lower alkyl having 1 to 3 carbon atoms; X is an acid residue; and a cyclohexyl ring in the above formula may have one double bond, production of the same and composition thereof. This invention relates to a quaternary ammonium salt having the following general formula:

United States Patent [191 Nakanishi et al.

[4 Nov. 26, 1974 METHOD FOR INHIBITING PLANT GROWTH WITH QUATERNARYAMMONIUM SALTS 75] Inventors: Kazuo Nakanishi; Hideo Yagi;

Takashi lwata; Hisae Haruta; Kazuhiko Yoshida; Akira Matui, all

211 App]. No.: 127,010

[30] Foreign Application Priority Data Apr. 6, 1970 Japan 45-29540 Mar.28, 1970 Japan 45-26098 Mar. 25, 1970 Japan 45-25544 Mar. 28, 1970 Japan45-26097 June 2, i970 Japan 45-48343 [52] U.S. Cl 71/12], 71/76, 71/88,

2,. v J112stzuazzswzsa299mm s.

[5]] Int. Cl AOIII 9/20 [58] Field of Search 71/76, 121

[56] References Cited UNITED STATES PATENTS 3.l56,555 ll/l964 Tolbert7l/l2l 3.506.433 4/l970 Abramitis et al. 71/78 3.580.7l6 5/l97l Mussellet al. 7l/76 FOREIGN PATENTS OR APPLlCATlONS 830,909 3/l960 GreatBritain Primary Examiner-Lewis Gotts Assistant Examiner-Catherine L.Mills 4 Attorney, Agent, or FirmOblon, Fisher, Spivak, McClelland &Maier [57] ABSTRACT This invention relates to a quaternary ammonium salthaving the following general formula:

wherein A is a lower alliyle ne, a lower alkenylene or a 7 loweralkadienylene; R and R are each lower alkyl which may be linked togetherdirectly or by an oxygen atom to form a saturated heterocyclic group; Ris a R and R are each lower alkyl having 1 to 3 carbon atoms; X is anacid residue; and a cyclohexyl ring in the above formula may have onedouble bond, production of the same and composition thereof.

41 Claims, No Drawings METHOD FOR INHIBITING PLANT GROWTH WITHQUATERNARY AMMONIUM SALTS This invention relates to a new quaternaryammonium salt, a process for preparing the same and a composition of thesame useful for regulating plant growth.

Accordingly, the present invention provides, as a novel compound, aquaternary ammonium salt of the formula:

wherein A is a lower alkylene, a lower alkenylene or a loweralkadienylene; R, and R are each lower alkyl which may be linkedtogether directly or by an oxygen atom to form a saturated heterocyclicgroup; R is a lower alkyl, a halo(lower) alkyl, a lower alkynyl, aphenyl(lower) alkyl which may have one or more halogen atoms assubstituents on the phenyl ring, a lower alkenyl, ahydroxy)lower)alkyll, a carboxy(lower)alkyl or a loweralkenyloxycarbonyl-(lower)alkyl; R R R are each lower alkyl having 1 to3carbon'atoms; X is an acid residue; and a cyclohexyl ring in the aboveformula may have one double bond.

It is to be understood, within the scope of the present invention, thatthe term lower" used in connection with alkyl, alkylene, etc. isintended to mean alkyl, al-

kylene, etc. having I to 10 carbon atoms unless othera wise indicated.

It is further to be understood, in this specification, that the loweralkylene covers methylene, ethylene, isopropylenefpropylene, butylene,isobutylene, pentylene, etc.; the lower alkenylene includes propenylene,l-methyl- 2-propenylene, 2-methyl-2 -propneylene, 2-methyl-2-butenylene, etc.; the lower alkaidenylene does 2,4-pentadienylene,3-methyl-2,4-pentadienylene, etc.; the lower alkyl includes methyl,ethyl, propyl, isopropyl, butyl, isobutyl, pentyl, isopentyl, hexyl,heptyl, octyl, etc.; the halo(lower)alkyl includes chloromethyl,bromomethyl, iodomethyl, chloroethyl, bromoethyl, iodoethyl,fluoromethyl, fluoroethyl, dichloromethyl, dichloroethyl, dibromomethyl,diiodomethyl, diodoethyl, chlorobromoethyl, chlorobromopropyl,chloropropyl, bromopropyl, iodoispropyl, etc.; the lower alkynylincludes 2-propynyl-(propargyl), butynyl, l-pentynyl, etc.; thephenyl(lower)alkyl includes benzyl, phenethyl, 3- phenylpropyl, etc.;the halogen includes fluorine, chlorine, bromine, iodine; the loweralkenyl includes vinyl, l-propenyl, 2- propneyl-(alkyhf l-butenyl,2-butenyl, 3-butenyl, lpentenyl. etc.; the hydroxy(lowcr)alkyl includeshydroxymet'hyl, 2- hydroxyethyl, l-hydroxyethyl, 3-hydroxypropyl.3-hydroxy-Z-methylpropyl, 4-hydroxybutyl, 2- hydroxybutyl, etc.; thecarboxy(lower)alkyl includes carboxymethyl, Z-carboxyethyl,3-carboxypropyl, 3-carboxy-2-methylpropyl, 4- carboxybutyl, etc.;

ethynyl, l-butynyl,

l-propynyl, 3-methyll Rt Rt I Ro,

and a cyclohexenyl ring, for eit ample, having the following formulae:

wherein R R and R are each lower alkyl having I to 3 carbon atoms.

The quaternary ammonium salt of the formula [I] has a plant growthregulating activity. Specifically, it has a plant growth inhibitingactivity due to its antigibbereliin and anti-auxin action in a plant.

Accordingly the compond [I] can be used as growth regulators toartificially control the growth of plants in agriculture andhorticulture and may be useful in various applications typicallyillustrated as follows:

Use to prevent elongation in the height of plants such as Italian ryegrass, orchard grass, sods, etc.; to prevent lodging of rice plant,wheat, etc. by inhibiting elongation; to dwarf the height of suchvegetables as cucumber, tomato, egg-plant, soybean, peas, kidney bean,Spanish paprika, etc. and flowers such as cosmos, sage, chrysanthemum,cyclamene, poinsettia, stock, morning glory, etc.; to prevent overgrowthof a pericarp of citrus fruits such as mandarin, orange, etc.; toinhibit growth of a naught lateral branch of vegetables such as melon,water melon, cucumber, tomato, egg-plant, etc. and fruit trees such aspear, grape, apple, grapefruit, citrus fruits, etc.; to prevent eargermination of cereals such as rice plant, wheat, etc. to accelerateenlargement in the root of edible roots such as radish, yam, onion,sweet potato, potato, chestnuts, carrot, burdock, etc.; to preventbolting of vegetables such as cabbage, white rape, carrot, radish,spinach, burdock, etc.; to alleviate frost damage, damage from adrought, damage from a salty wind or damage from a hotness, of fruitssuch as Japanese persimmion, grape, mulberry. etc. and vegetables suchas green pea, spinach, lettuce, etc.; to accelerate ripeness of fruitssuch as mandarin apple. peach, grape, tomato, cherry, strawberry, etc.;

to accelerate female flower bud formation ofcucumher, water melon,melon, pumpkin, etc. to induce flower-bud formation of flowers such asmorning glory, cosmos, salvia, potmum, etc. and fruits such as apple,peach, grape, persimmon, etc.;

The compound [I] may be further expected to be useful in variousapplications as follows:

Use to prevent head cracking of globose vegetables such as cabbage,etc.; to prevent cracking of fruits such as grape, cherry, apple, etc.;to prevent overripening of water melon, melon, etc.; to preventsprouting of plants such as potato, sweet potato, yam, onion, chestnuts,etc. during storage thereof;

to prevent generation and growth of auxiliary buds of tobacco plant,particularly after pinching of terminal bud; to improve storageabilityof cereals such as rice, wheat, corn, etc., fruits such as apple, etc.,vegetables such as onion, yam, potato, sweet potato, etc., and otherseeds or crops; to prevent malformation of egg-plants caused by sideeffect of some agricultural chemicals; to accelerate vernalization, ascontrol of a flower-bud formation, of plants such as grape, mandarin,apple, peach, barley, rye, wheat, etc.; to prevent dropping of fruitssuch as apple, mandarin, peach, pear, etc.

According to the present invention, the quaternary ammonium salt of theformula:

Re El wherein A is a lower alkylene, a lower alkenylene or a loweralkadienylene; R, and R are each lower alkyl which may be linkedtogether directly or by an oxygen atom to form a saturated heterocyclicgroup; R is a x/ wherein A, R., R R R and R are the same as definedabove; and a cyclohexyl ring in the above formula may have one doublebond, with a compound of the formula:

wherein A is a lower alkylene, a lower alkenylene or a loweralkadienylene; R and R are each lower alkyl, which may be linkedtogether directly or by an oxygen atom to form a saturated heterocyclicgroup; R R and R are each lower alkyl having l to 3 carbon atoms; andthe cyclohexyl ring in the above formula may have one double bond,

is prepared by reacting a compound of the formula:

wherein A, R,, R and R are the same as defined above; and the cyclohexylring in the above formula may have one double bond, or its reactivederivative at the carboxyl group, with an amine of the formula:

wherein R and R are the same as defined above, and then reducing theresulting compound of the formula:

R2 Re wherein A, R R R R and R are the same as defined above; andcyclohexyl ring in the above formula may have one double bond with areducing agent selected from an alkali metal boron hydride, an alkalimetal lithium hydride, and a combination of alkali metal and alcohol.

b. A tertiary amine of the formula:

v the above formula may have one double bond, with an wherein A is alower alkylene, a lower alkenylene or a lower alkadienylene; R and R areeach lower alkyl which may be linked together directly or by an oxygenatom to form a saturated 5 heterocyclic group; R r and R are each loweralkyl having 1 to 3 carbon atoms; and the cyclohexyl ring in the aboveformula may have one double bond,

is prepared by reacting a compound of the formula: 10

Ru I

wherin the, R R and'R are the same as defined above; X is an acidresidue; and a cyclohexyl ring in amine of the formula:

wherein R and R are the same as defined above. c. A tertiary amine ofthe formula:

wherein A is a lower alkylene, a lower alkenylene or a loweralkadienylene; R, and R are each lower alkyl which may be linkedtogether directly or by an oxygen atom to form a saturated heterocyclicgroup; R R and R are each lower alkyl having l to 3 carbon atoms; R is ahydrogen or a lower alkyl; and the cyclohexyl ring in a above formulamay have one double bond, is prepared by reacting formic acid and anamine of the formula:

wherein R, and R are the same as defined above, with .a compound of theformula:

addition salt such as sodium chloride, potassium chloride, sodiumbromide, potassium bromide, sodium iodide, potassium iodide, silverchloride, silver bromide, silver iodide etc., a quarternary ammoniumsalt [I 1 having an acid residue of the metal acid additon salt insteadof an acid residue of a compound [Ill may be obtained. When the presentreaction is carried out in the presence of sodium iodide, potassiumiodide or the like, such compound may promote the present reaction.There is no limitation as to the reaction temperature.

The quaternary ammonium salt [I of the present invention is rarelyapplied directly onto plants, and used in the form of compositionscomprising at least one of the quaternary ammonium salt of the formula[l in association with a carrier, or a surface-active agent, or both acarrier and a surface-active agent. The effectiveness of the compound ofthe present invention, when the compound is used as plant growthregulators, will depend on the concentration applied. Considerableranges of an effective concentration of the quaternary ammonium salt [Ias plant growth regulators will be observed depending not only on thekind, organ or texture of plants to be treated, but also on thephysiological age of the plants. Thus, the concentration to be employedshould be determined suitably depending on the intended use of theagent, the type of plants to be treated and the period of application.Usually the effective concentration, however, will be within the rangeof 1 5000 ppm and preferably of 10 500 ppm, and although these are notcritical.

Now the plant growth regulating activity of typical compounds which fallwithin the category of the compound of the formula [I 1 of thisinvention is illustrated by reference to various tests in whichindividual active ingredients are the following numbered compounds.Compound No. l

[3-methyl'-5-(2,6,6-trimethyl-l-cyclohexenyl)-2,4-pentadienyl]trimethylammonium iodide Compound No. 2

[l-methyl-3-( 2,6,6-trimethyl-2-cyclohexenyl)-2-propenyl]trimethylammonium iodide Compound No. 3

[l-methyl-3-( 2,6,6-trimethyll -cyclohexenyl)- propyl]trimethylammoniumiodide Compound N0. 4

[3-(2,6,6-trimethyl-l-cyclohexenyl)-2-propenyl]- trimethylammoniumiodide Compound No. 5

l-methyl-3-(2,6,6-trimethylcyclohexyl)propylltrimethylammonium iodideCompound No. 6

[1-methyl-3-(2,6,6-trimethyl-2-cyclohexenyl)-2-propenyl]dimethylpropylammonium iodide Compound No. 7

[l-methyl-3-(2,6,6-trimethyI-Z-cyclohexenyl)-2-propenylldimethylethylammonium iodide Compound No. 8

[1-methyl-3-(2,6,6-trimethylcyclohexyl(propyl]- trimethylammoniumbromide Compound No. 9

[l-methyl-3-( 2,6,6-trimethyl-Z-cyclohexenyl)-2-propenyl]trimethylammonium chloride Compound No. 10

[1-methyl-3-( 2,6,6-trimethyl-2-cyclohexenyl)-2-propenyl]trimethylammonium bromide Compound No. 11

l-methyl-3-(2,6,6-trimethylcyelohexyl)propyl]- dimethyl(3,4-dichlorobenzyl)ammonium iodide Compound No. 12

4-methyl-4-[ l-methyl-3-(2,6,6-trimethyl-2-cyclohexenyl)-2-propenyl]morpholinium iodide Compound No. 13

[1-methyl-3-(2,6,6-trimethyl-Z-cyclohexenyl)-2-propenyl]dimethylpropargylammonium iodide Compound No. 14

[i-methyl-3-(2,6,6-trimethyl-2-cyclohexenyl)-2-propenyl]dimethylheptylammonium iodide Compound No. 15

l-methyl-[ l-m ethyl-3-( 2,6,6-trimethyl-2-cyclohexenyl)-2-propenyl]piperidinium iodide Compound No. 16

[l-methyl-3-(2,6,6-trimethyl-2-cyclohexenyl)-2-propenyl]dimethyl(2-propenyl)ammonium iodide Compound No. 17

[l-methyl-3-( 2,6,6-trimethyl-2-cyclohexenyl)-2-propenyl]dimethyl(2-hydroxyethyl)ammonium dide Compound No. 18

[l-methyl3-(2,6,6-trimethyl-l-cyclohexenyl)-2-propenyl]trimethylammonium chloride Compound No. 19

[l-methyl-3-( 2,6,o-trimethyl-2-cyclohexenyl)-2-propenyl]dimethyl(2,4-dichlorobenzyl)ammonium iodide Compound No. 20

[l-methyl-3-(2,6,6-trimethyl-l-cyclohexenyl)-2-propenyl]dimethyl(2,4-dichlorobenzyl)ammonium iodide Compound No. 21

[l-methyl-3-(2,6,6; -trimethyl-l-cyclohexenyl)-2-propenyl]dimethylheptylammonium iodide Compound No. 22

[l-methyl-3-(2,6,o-trimethyl-2-cyclohexenylZ-propenyl]dimethylheptylammonium iodide Compound No. 23

[l-methyl-3-( 2,6,6-trimethyll -cyclohexenyl)-2-propenyl]dimethyl(3,4-dichlorobenzyl)ammonium iodide Compound No. 24

[l-methyl-3-(2,6,6-trimethyl-2-cyclohexenyl)-2-propenyl]dimethyl(3.4-dichlorobenzyl)ammonium iodide Compound No. 25

[l-methyl-3-(2,6,6-trimethyl-l-cyclohexenyl)-2-propenyl]dimethyl(4-chlorobenzyl)ammonium iodide Compound No. 26

[l-methyl-3-(2,6,6-trimethyl-2-cyclohexenyl)-2-propenyl]dimethyl(4-chlorobenzyl)ammonium iodide Compound No. 27

[l-methyl-3-(2,6,6-trimethyl-2-cyclohexenyl)-2-propenyl]dimethyl(4-chlorobenzyl)ammonium chloride Compound No. 28

[l-methyl-3-(2,6,6-trimethylcyclohexyl)propyl1- dimethyl(2.4-dichlorobenzyl)ammonium chloride Compound No. 29

ll-methyl-3-(2,6,6-tirmethyl-2-cyclohexenyl)-2-propenyl]dimethyl(3,4-dichlrobenzyl)ammonium bromide Compound No. 30

bro-

Compound No. 35

l-methyl-3-(2,6,6-trimethyl-2-cyclohexenyl)-2-propenyl]dimethyl(3,4-dichlorobenzyl)ammonium bromide.

Test 1.

Ten ml. of an aqueous solution of the test compound mentioned below witha specified concentration was poured into a glass tube of l0-cm. lengthand 3-cm. diameter. Ten rice seeds germinating slightly were placedtherein and were allowed to grow for 6 days at 25 1*: lC under a 300-luxlight preventing the evaporation of water. Then, the length of thesecond leaf sheath was measured. The results are set forth in thefollowing table, in which the elongation ratio (percent) is expressed asa relative value when the elongation of control plant in thenon-treatment area is rated as 100.

Compound Concentration (ppm) No. 200 100 50 I0 I 1 I6 54 73 87 H5 2 0 3548 76 86 3 42 44 59 88 82 4 29 58 61 83 86 5 0 57 62 86 I00 6 O 53 63I00 95 7 0 53 68 89 95 ll 0 O 67 87 100 l6 0 72 97 98 IO] 9 HP 29 46 7399 8 28 54 75 i0 82 93 l2 34 59 79 83 I3 31 60 83 89 14 42 53 62 64 1520 43 63 67 I7 54 67 77 79 I9 79 89 21 22* 34 56 74 78 23 24* 54 63 7I72 25 26* 62 7O 76 78 27 82 88 93 94 28 40 62 79 83 29 6] 73 82 84 31 5669 79 81 32 57 70 81 83 ('Nmc: The solution coutuins the lwo kind ofcompounds at the equivalent ummlnbl Test 2.

Five ml. of an aqueous solution of the test compound mentioned belowwith a specified concentration was poured into a glass tube of l-cm.length and 3-cm. diameter, and an aqueous solution of gibberellin (20ppm) was added thereto. Ten rice seeds germinating slightly were treatedin a similar manner to Test 1, and the length of the second leaf sheathwas measured. The results are set forth in the following table, in whichthe elongation ratio (percent) is expressed as a relative value when theelongation of the control plant which was treated with gibberellin (20ppm) alone is rated as l00.

(Notct The solution contains the two kinds of compounds at theequivalent amount.)

Test 3.

Five ml. of an aqueous solution of the test compound mentioned belowwith a specified concentration was poured into a petri dish of 7-cm,diameter having a filter paper at the bottom. Ten seeds each of rice andPanicum sp. were placed in each of two petri dishes, and were allowed togrow under a 300-lux light for 10 days at 24C. Then the height of plantand length of the root were measured respectively. The results are setforth in the following table, wherein the root length and height of theplants are expressed as a relative value (percent) when those of thecontrol plants in the nontreatment area are rated as 100.

Com- Conc. Rice Panicum sp.

pound No. (ppm) Root length Height Root length Height 100 I3 42 3 72 520 65 57 50 Ill 4 86 83 I20 130 100 19 57 66 6 20 52 64 63 108 4 95 110103 l l l 100 ll Z8 17 62 7 20 43 40 77 90 4 76 77 150 111 100 14 30 27ll 12 2O 43 83 67 ll] Test 4.

Five ml. of an aqueous solution of the test compound mentioned belowwith a specified concentration was poured into a petri dish of 9-cm.diameter having a filter pater at the bottom. Seven seeds of cucumberwere placed therein, and were kept at 30C. for 48 hours. The seeds werefurther allowed to grow for 10 days at 24': 1C. under a 300-lux light.The length of the hypocotyl was measured. The results are set forth inthe following table, wherein the elongation ratio (percent) is expressedas a relative value when the elongation of the control plant is ratrated as 100.

Seeds of cucumber were sowed in a porous pot.

When the average length of foliage leaves became 1.5

cm., the length from the base of copyledon up to the growth point wasmeasured this length is referred to as a symbol A in the table and anaqueous solution of the test compound mentioned below with a specifiedconcentration was sprayed onto leaves. Ten days after, the length fromthe base of copyledon up to the growth point this length is referred toas a symbol B in the table and the same test solution as mentioned abovesprayed again. After a lapse of an additional 20 days, the length fromthe base of copyledon up to the growth point was measured this lengthwill hereinafter be referred to by a symbol C" in the table. Values ofB/A and C/B were calculated for each compound. The same calculation asmentioned above was also conducted for the control in which the plantswere not treated with the test compound. The figure in the table meansthe percent (percent) of the calculated value or the treatment area tothe calculated one on the control. The results ai'e set forth in thefollowing table.

Cucumber seeds were sowed in a flowerpot of l0-cm diameter. When thenumber of foliage leaves is 1.5 in average, an aqueous solution of thetest compound mentioned below with a specified concentration was sprayedonto the leaves. When the average number of foliage leaves was 3, thesolution mentioned above was sprayed again. Fifty days after sowing, theheight up to the 15th node, the number of leaves, the overall height ofthe plants and the average internode distance were measured. The resultsare set forth in the following table, wherein the growth ratio (percent)is expressed as a relative value to the control plants in thenontreatment area.

Slightly germinating seeds of Pisum sp. were sowed in a flowerpot ofl-cm. diameter. After a lapse of 15 days, the length from the base ofthe scaly leaf to the growth point was measured this length willhereinafter be referred to by the symbol A". and an aqueous solution ofthe compound mentioned below with a specified concentration was sprayedonto leaves. Seven days thereafter, the length from the base of thescaly leaf to the growth point was measured this length will hereinafterbe referred to by a symbol B and the test solution as mentioned abovewas sprayed again. Seven days afterwards, the length from the base ofthe scaly leaf to the growth point was measured this length ishereinafter referred to as a symbol C. Values of B/A, C/A and C/B werecalculated for each compound. The same calculation as mentioned abovewas conducted for the control in which the plants were not treated withthe test compound. The figure in the table means the percent (percent)of the calculated value on the treatment area to the calculated one onthe control. The results are set forth in the following table.

Com- Concentration (Dom) pound 500 I00 No B/A CIA C/B BIA C/A C/B Test8.

Compound Concentration {ppm} No. 200 I00 50 l0 1 (Note: The testsolution contains two kinds of the compounds at the equivalent amount.)

Test 9.

Seeds of cucumber were allowed to grow under the same conditions asshown in the Test 1 except for using an aqueous solution of the compoundmentioned below with a specified concentration. The length of thehypocotyl was measured. The results are set forth in the followingtable, wherein the elongation ratio (percent) is expressed as a relativevalue to the contro.

Seeds of cucumber were sowed in mid January. Thirty four days after,seedlings were transplanted in a greenhouse. When the plants had tenfoliage leaves in agera'ge, i.e., 19 days after transplantation, anaqueous solution of the test compound No. 2 with a concentration of 25ppm was sprayed onto the leaves. Twenty two days after spray, the heightof plants was measured. After the plants were further grown, the totalyield (g) of cucumbers harvested 125 days after sowing was weighed. Theresults are shown as follows.

Compound No. Height (cm) Yield (g) Control 133 9,690

Test 1 1.

Seeds of cucumber were sowed in mid December. When the plants had 2leaves on the average, i.e., 27 days after sowing, an aqueous solutionof the test compound with a specified concentration was sprayed onto theleaves. Thirty seven days after sowing, seedlings were transplanted to agreenhouse. After days, the

internode lengths between the lst node and the 15th house. The followingitems were observed on the specione, between the 1st node and the 30thone and befied day as given in the table tween the 1st node and theupper one respectively were measured At the Same time the total numberof nodes (A) Observation of growth days after transplantation.

female flowers and fructifying branchs were counted, 5

and then the states of yield were examined. The results Heigh' 2f g L noe earmg t e are set forth in the following tables. (ppm) first flowercluster 32.3(8l.6) 8.] 2 (A) lnternode lengths 10 25 329ml) c C Tom]Control 39.6 I00) 3.4

im one th 30th 30! numbers (Note: The figure in parenthesis means arelative value (54 I to the control.)

(ppm) node (74) node (7:) node (Z) nodes'(7r) N r Hm fl M 50 75.4 88.087.5 84.7 15 2 (B) States of yield during 138 days aftertransplantation.

Compound Cone. No. of fruit harvested 50 88.9 93.3 92.6 89.3 lst fruit2nd fruit 3rd fruit 4 No. (ppm) cluster cluster cluster 3.6 L2 0 50 71.684.3 83.3 83.7 Comm 25. Compound Conc. Avera e Wei ht of fruit lst fruit2nd fruit 3rd fruit [49.3 276.6 295.] 48.4 No. (ppm) cluster clustercluster Control cm cm cm (Now (I 0) (100) (I00) 100 7 10 132 197 itstreatmenu 25 114 I58 128 Control 143 110 90 Note :The figure means arelative value ('6 l to the control.

(8) Ratio of female flower Number and the states of yield:

Compound Conc. lst-lOth node llth-ZOth node 2ith-30th node Number of-The position of branch node bearing bearing fruits the first female No.(ppm) A B A B A B flower so 42 92 70 98 i 88 6.7 3.5 2

I00 43 37 93 77 98 92 l0.0 3.8 43 42 85 93 83 l3.0 3.7 4 I00 33 22 92 5092 8.3 5.8 50 35 32 93 52 98 87 3.3 5.8 5

. I00 28 20 90 63 lOO 87 3.3 6.5 Control 32 28 72 62 88 75 4.2 4.8

(Nontreatment) Note: In the above table. A refers to ratio of femaleflower number" which is calculated from the following formula:

Number of female flower A x 100 Number of node and B refers tofructification percent per one node which is calculated from thefollowing formula:

Number of fructification A x 100 Number of node Test 12. Test 13.

Seeds of tomato were sowed at the end of October. S d f t t w w d i midDecember, and when the plants had 6 foliage leaves on the average, 45days afterward, an aqueous solution f Compound i.e. 48 days aftersowing, an aqueous solution of the N 19 (200 ppm) was sprayed onto theplant having compound mentioned below with a specified concensix foliageleaves. Seedlings were transplanted to a tration was sprayed onto theplants. Twenty five days greenhouse. Fifteen days after transplantation,the after spraying seedlings were transplanted into a greenplants wereallowed to growby means of a gravel culture provided with undergroundheating facility, and the yield in both weight and number of fruitsharvested during subsequent 124 days was observed.

Compound Cone. Total Total Average No. of weight weight per No. (ppm) Ifruit (kg) fruit (g) Control 10.83 1.52 140 Test 14.

Seeds of spinach were sowed at the end of November. An aqueous solutionof Compound No. 2 (100 ppm) was sprayed to plants 88 days thereafter.height of plants and length of stems, respectively, were measured 17days after spraying. The results 100 ppm) was sprayed to plants 88 daysthereafter. height measured 17 days after spraying. The results are setforth in the following table.

Compound Conc. Height Stem length No. (ppm) (cm) (cm) Control 35.5 40.2

Test 15.

An aqueous solution of the compound mentioned below with a specifiedconcentration was sprayed onto one of branches 1 m. in length of anapple tree at the .end of May. The items mentioned in the followingtable were observed.

Compound No. Cone. (ppm) A (71) B ('2) Control 161.0 264.3

Note:

it"A" in the tuhlc refers to "the elongation ratio ('1 lotcurrent yourshoot" which is calculated according to the following formulu.

A (percent) The length of the current year shoot at 1 the time of theelongation stopping X100 The length of the current year shoot at thetime of spray of the test solution In this test, the measurement wasconducted 99 days after the spray of the test solution.

2. B" in the table refers to growth ratio of fruit which is calculatedaccording to the following formula.

B (percent) Diameter of fruit 113 days after spray v Diameter of fruitat the time of the spray of the test solution Test 16.

An aqueous solution (500 ppm) of the compound No. 2 was sprayed onto 5branches of a grape bearing female buds at the 20th day before the fullbloom thereof. The elongation ratio (percent) of the current year shootcompared with the length of the current year shoot at the time ofspraying was measured at the 50th day after spraying, and the fruitsharvested during days after spraying was weighed.

Elongation ratio of the Compound Fruits weight No. current year shoot(Z') Control 611.4 232.4

Test 17.

An aqueous solution (200 ppm) of the compound No. 2 was sprayed ontobranches of a mandarin tree bearing fruits at the end of December. Thestate of over growth of pericarp of mandarins was measured at the 25thday after spraying. The results are set forth in the following table.

State of pericarp in mandarin (71) Compound No.

Non Slight Me- Remarkable dium Control 48.4 46.2 5.0 0 lll.7

1n the above table, A refers to a index of pericarp of mandarin which iscalculated according to the following formula:

(No. of non) (No. of mediumX 2) (No. of remarkab1e 3) Total fruit number3 Height Flower diameter Compound Conc.

No. (ppm.) cm 71 cm k Practical and presently-preferred embodiments forthe preparation of the compound [11] are illustratively shown in thefollowing examples.

1. Preparation of[3-methyl-5-(2,6,6-trimethyl-lcyclohexenyl)-2(trans),4(trans)-pentadienyl]dimethylamineA solution of 3-methyl-5-(2,6,6-trimethyl-1-cyclohexenyl)-2(trans),4(trans)-pentadienoic acid (4.5 g) in absolutebenzene (60 cc) was added to thionylchloride (5.8 g) under cooling andthe mixture was allowed to stand for 2 hours at room temperature. Theexcess thionylchloride was distilled off under reduced pressure, and theresidue was dissolved in absolute benzene (30 cc). The mixture was addeddropwise to a mixture of dimethylamine (20 cc) and absolute benzene cc)under cooling, and the mixture was allowed to stand for 2 hours. Thereaction mixture was washed with water and dried over magnesium sulfate.The solvent was distilled off, and the oily residue was distilled at 138143C under reduced pressure (0.3 mmHg) to give an oil (2.6 g) ofN,N-dimethyl-3- methyl-5-(2,6,6-trimethyl-1-cyclohexenyl)-2(trans),4(trans)-pentadienoic acid amide. To a solution of lithiumaluminium hydride (0.5 g) in dry ether (25 cc) was added dropwise asolution of N,N- dimethyl-3-methyl-5-(2,6,6-trimethyl-lcyclohexenyl)-2(trans),4(trans)-pentadienoic acidamide (2.5 g) in dry ether (25 cc) under cooling, and the reactionmixture was refluxed for 2 hours. Thereto was added water in order todecompose the excess 1ithium aluminium hydride, and the reaction mixturewas filtered. The filtrate was extracted with ether and the ether layerwas dried. The solvent was distilled off, and the residue was distilledat 1 18- 124C under reduced pressure (0.8 mmHg) to give an oil (1.3 g)of [3- methyl-5-(2,6,6-trimethyl-l-cyclohexenyl)-v2(trans),4(trans)-pentadienyl]-dimethylamine.

2. Preparation of [3-(2,6,6-trimethyl-l-cyclohexenyl)-2(trans)-propenylldimethylamine To a solution of3-(2,6,6-trimethyl-l-cyclohexenyl)- 2(trans)-acrylic acid (5.0 g) in drybenzene cc) was added thionylchloride (10 cc) at room temperature, andthe mixture was allowed to stand over night. The excess thionylchloridewas distilled off under reduced pressure, and the residue was dissolvedin dry ether (20 cc), and the ethereal solution was added dropwise to asolution of dimethylamine (5.0 g) in ether (20 cc) under cooling at 0Cduring 10 minutes. The mixture was stirred for 2 hours, washed withwater and dried.

The solvent was distilled off under reduced pressure to washed withether. The aqueous solution was adjusted to an alkalinity by adding anaqueous solution of sodium hydroxide and extracted with ether. The etherlayer was washed with an aqueous solution of sodium chloride and dried.The solvent was distilled off under reduced pressure. The residue wasdistilled at 98 99C under reduced pressure (5 mmHg) to give a colorlessoil (4.0 g) of [3-(2,6,6-trimethyl-1-cyclohexenyl)-2(trans)-propenylldimethylamine. 3. Preparation of4-[1-methyl-3-(2,6,6-trimethyl-2-cyclohexenyl)-2(trans)-propenyl]morpholine A solution of1-methyl-3-(2,6,6-trimethyl-2- cyclohexenyl)-2(trans)-propenol in amixed solvent of dry ether (200 cc) and pyridine (4 cc) was addeddropwise to a solution of phosphorus tribromide (29.6 g) in dry ethercc) under cooling at below 10C. The mixture was stirred for 5 hours at 510C and allowed to stand over night. The mixture was poured intoicewater, and the organic layer was washed with water and dried. Theorganic layer was added dropwise to a solution of morpholine (26.7 g) indry ether (80 cc) under cooling, and the reaction mixture was stirredfor 5 hours under cooling at 5 10C. The mixture was washed with waterand extracted with hydrochloric acid. The extract was adjusted to analkalinity by adding an aqueous solution of sodium bicarbonate andextracted with ether. The ether layer was washed with water and dried.The solvent was distilled off under reduced pressure, and the residuewas distilled under reduced pressure (1 mmHg) at 128 130C to give an oil(8.2 g) of 4-[1-methyl-3-(2,6,6-trimethyl-2-cyclohexenyl)-2(trans)-propenyl]morpholine. 4. Preparation of1-[1-methy1-3-(2,6,6-trimethyl-2-cyclohexenyl)-2(trans)-propenyl]piperidine With a mixture of1-methyl-3-(2,6,6-trimethyl-2- cyclohexenyl)-2(trans)-propenol (10.0 g),phosphorus bromide (74 g) and piperidine (6.6 g), an oil (3.0 g) of 1-[l-methyl-3-(2,6,6-trimethyl-2-cyclohexenyl)-2(trans)-propenyllpiperidine, b.p. 143 149C (1 mmHg), was obtainedaccording to a similar manner to the preceding preparation 3. 5.Preparation of [l-methyl-3-(2,6,6-trimethyl-2-cyclohexenyl)-2(trans)-propenylldimethylamine A solution ofl-methyl-3-(2,6,6-trimethyl-2- cyclohexenyl)-2(trans)-propenol (30.0g)and piperidine (2.6 cc) in absolute ether cc) was added dropwise to asolution of phosphorus tribromide (20.0 g) in absolute ether (100 cc)under cooling at 5 10C. The reaction mixture was stirred for severalhours and allowed to stand over night. Thereto was added water, and theaqueous solution was extracted with ether. The ether layer was washedwith an aqueous solution of sodium bicarbonate and dried over magnesiumsulfate. The solvent was distilled off, and the residue was dissolved inehter 100 cc). Thereto was added dropwise a solution of dimethylamine(12.4 g) in ether (50 cc) during 4 hours under cooling, and the reactionmixture was stirred for 24 hours at room temperature. The reactionmixture was poured into ice, and the mixture was acidified by addinghydrochloric acid. The aqueous layer was alkalized by adding an aqueoussolution of sodium hydroxide, and then the mixture was extracted withether. The ether layer was washed with water and dried over magnesiumsulfate. The solvent was distilled off under reduced pressure and theoily residue was distilled at 95 96C under reduced pressure (3mmHg) togive an oil of [l-methyl-3-(2,6,6- trimethyl-Z-cyclohexenyl)-2(trans)propenylldimethylamine.

Analysis: C H N Calculated C 81.37, H 12.30, N 6.32 Found C 81.20, H12.17, N 6.54.

6. Preparation of a mixture consisting of 1-[ 1-methyl-3-(2,6,6-trimethyl-2-cyclohexenyl)-2- propenyllpyrrolidine and l[l-methy13-(2,6,6- trimethyll -cyclohexenyl)-2-propenyl pyrrolidine Amixture of 4-(2,6,6-trimethyl-2-cyclohexenyl)-3- butene-Z-one (19.2 g),formylpyrrolidine (30.0 g) and formic acid (15.0 g) was sealed andheated at 190C for 6 hours. After the completion of the reaction, thereaction mixture was acidified by adding 10 percent hydrochloric acidand was washed with ether. The reaction mixture was alkalized by addingdil. aqueous solution of sodium hydroxide, and then extracted withether. The ether layer was dried and the solvent was distilled off. Theoily residue was distilled at 161 163C under reduced pressure (12 13mmHg) to give an oily mixture (6.0 g) consisting of1-[1-methy1-3-(2,6,6- trimethyl-l-cyclohexenyl)-2-propenyl]pyrrolidineand 1-[1-methy1-3-(2,6,6-trimethyl-Z-cyclohexenyl)-2-propenyll-pyrrolidine.

It was observed in the IR. spectrum of this oil that the absorption at1665 cm-1 based on the carbonyl group, which was existing in the fromthat of 4-(2,6,6- trimethyl-Z-cyclohexenyl)-3-butene-2-one, hasdisappeared.

Analysis: C11H29N Calculated C 82.52, H 11.18, N 5.66

Found 2 C 82.38, H 11.61, N 5.64.

7. Preparation of a mixture consisting of [l-methyl-3-(2,6,6-trimethyl-1-cyclohexenyl)-2- propenylldimethylamine and[l-methyl-3-(2,6,6- trimethyl-Z-cyclohexenyl)-2-propenyl]dimethylamine Amixture of 4-(2,6,6-trimethyl-l-cyclohexenyl)-3- butene-Z-one (33.4 g),dimethylformamide (43.8 g) and formic acid (27.6 g) was sealed andheated at 190C for 14 hours. After the completion of the reaction, thereaction mixture was dissolved in dil. hydrochloric acid and the aqueoussolution was washed with ether. The aqueous solution was alkalized byadding dil. aqueous solution of sodium hydroxide and extracted withether. The ether layer was washed with water, dried and the solvent wasdistilled off under reduced pressure. The oily residue was distilledunder reduced pressure (33mHg) at 103 104C to give an oily mixtureconsisting of[ l-methyl-3-(2,6,6-trimethyl-1-cyc1ohexenyl)-2-propenylldimethylamine and[lmethyl-3-(2,6,6-trimethy12-cyclohexenyl)-2- propenylldimethylamine1:1).

It was observed in the LR. spectrum of this oil that the absorption at1665 cm-1 based on the carbonyl group. which was existing in that of4-(2,6,6-trimethyl- 2-cyclohexenyl)-3-butene-2-one, has disappeared.Analysis: C H N Calculated C 81.75, H 11.89, N 6.34

Found C 81.87, H 12.23, N 6.49.

Practical and presently-preferred embodiments for the preparation of thepresent invention are illustratively shown in the followingnon-limitative examples.

EXAMPLE 1 a. To a solution of [1-methy1-3-(2,6,6-trimethylcyclohexyl)propyl]dimethylamine (3.0 g) in benzene (20 cc) wasadded methyliodide (10.0 g), and the mixture was allowed to stand overnight. precipitated crystals were gathered by filtration, andrecrystallized from a mixed solvent of benzene and ether to givecolorless crystals (4.4 g) of [1-methy1-3-(2,6,6-

trimethylcyclohexyl)-propy1ltrimethylammonium dide. N.M.R. spectrum:

'1 9.00 9.23 9H '1' 8.50 (doublet) 3H 1' 6.58 (singlet) 9H b. A mixtuureof [l-methyl-3-(2,6,6-

trimethylcyclohexyl)propyl]trimethylammonium iodide (5.0 g), silverbromide (5.0 g) and absolute methanol (10 cc) was refluxed for 3 hours,and the reaction mixture was filtered. The filtrate was concentrated andthe concentrate was recrystallized from a mixed solvent of benzene andether to give colorless crystals (3.6 g) of[1-methyl-3-(2,6,6-trimethylcyclohexyl)pr0pyl]- trimethylammoniumbromide.

N.M.R. spectrum:

1' 9.00 9.23 9H 1 8.50 (doublet) 3H 1' 6.60 (singlet) 9H c A mixture of[1-methy1-3-(2,6,6-

trimethylcyclohexyl)propyl]trimethylammonium iodide (5.0 g) and silverchloride (6.0 g) was treated according to a similar manner to theExample 1 (b), and colorless crystals (2.3 g) of [l-methyl-3-(2,6,6-trimethylcyclohexyl)propyl]-trimethylammonium chloride were obtained.

N.M.R. spectrum:

1 8.48 (doublet) 3H 1' 6.57 (singlet) 9H EXAMPLE 2 1 9.00 (singlet) 6H1' 8.44 (doublet) 3H 7 8.33 (singlet) 3H r 6.60 (singlet) 9H -r= 6.10(multiplet) 1H EXAMPLE 3 a. Crystals (4.5 g) of1-methyl-3-(2,6,6-trimethyl-2-cyclohexenyl)-2(trans)-propenyl]trimethylammonium iodide, m.p. C, wereobtained by treating [1-methyl-3-(2,6,6-trimethyl-2-cyclohexenyl)-2(trans)-propenyfldimethylamine (3.0 g) similarly to the Exam ple 1 (a).

Analysis: C H NJ Calculated C 52.89, H 8.32, N 3.85, .1 35.57

Found C 52.86, H 8.50, N 3.83, J 35.48. N.M.R. spectrum:

r= 9.16 (doublet) 3H -r= 9.10 (singlet) 3H 1' 8.44 (multiplet) 6H 1'6.63 (singlet) 9H 1= 5.40 (multiplet) 1H 1' 3.7 4.72 (multiplet) 3H b. Asolution of [l-methyl-3-(2,6,6-trimethyl-2cyclohexenyl)-2(trans)-propenylltrimethylammonium iodide (2.0 g) andsilver bromide (3.0 g) in absolute methanol cc) was treated according toa similar manner to the Example 1 (b), and the concentrate thus obtainedwas recrystallized from a mixed solvent of ethanol and ether to givecolorless crystals (1.2 g) of[1-methyl-3-(2,6,6-trimethyl-Z-cyclohexenyl)-2(trans)-propenylltrimethylammonium bromide, m.p. 258 260C.

Analysis: C H NBr Calculated Br 25.26 Found Br 25.21.

N.M.R. spectrum:

-r= 9.15 (singlet) 3H 1 9.08 (singlet) 3H 1' 8.44 (multiplet) 6H 1 6.60(singlet) 9H 1' 5.40 (multiplet) 1H r=3.804.80 3H c. A solution of[l-methyl-3-(2,6,6-trimethyl-2-cyclohexeny1)-2(trans)-propenyl]trimethylammonium iodide (2.0 g) andsilver chloride (3.0 g) in absolute methanol (10 cc) was treatedaccording to a similar manner to the Example 1 (b), and the concentratethus obtained was recrystallized from a mixed solvent of ethanol andether to give colorless crystals (1.0 g) of[1-methyl-3-(2,6,6-trimethyl-2-cyclohexenyl)-2(trans)-propenyl]trimethylammonium chloride. Analysis: C, H NClCalculated C 70.69, H 11.12, N 5.15, Cl13.04

Found C 70.45, H 11.30, N 5.39, Cl 12.82. N.M.R. spectrum:

1' 9.20 (singlet) 3H 1- 9.10 (singlet) 3H 1 8.44 (multiplet) 6H 1' 6.60(singlet) 9H 1' 5.40 (multiplet) 1H 1 3.80 4.80 (multiplet) 3H EXAMPLE 4With a solution of [1-methyl-3-(2,6,6-trimethyl-2-cyclohexenyl)-2(trans)-propenylldimethylamine (5.4 g) and ethyliodide(15.0 g) in benzene cc), colorless crystals (5.6 g) of[1-methyl-3-(2,6,6-trimethyl-2-cyclohexenty)2(trans)-propenyl]dimethylethylammonium iodide, mp. 133C,were obtained according to a similar manner to the Example 1 (a).

Analysis: CnHagNJ Calculated C 54.11. H 8.55, N 3.71, .l 33.63

Found C 54.19, H 8.40, N 3.54, .1 33.61. N.M.R. spectrum:

(doublet) (singlet) -Continued 1- 6.76 (singlet) 6H 1 6.32 (quartet) 2H1 5.40 (multiplet) 1H EXAMPLE 5 A mixture of[1-methyl3-(2,6,6-trimethyl-2- 0cyclohexenyl)-2(trans)-propenylldimethylamine (2.3

g) and ethylbromide (6.0 g) was refluxed for 3 hours, and then theexcess ethylbromide was distilled off. The residue was recrystallizedfrom a mixed solvent of benzene and ether to give colorless crystals(0.9 g) of [1- methyl-3-(2,6,6-trimethyl-Z-cyclohexenyl)-2(trans)-propenyl]dimethylethylammonium bromide. Analysis: C H NBr Calculated C61.81, H 9.76, N 4.24, Br 24.19 Found C 61.17, H 9.64, N 4.09, Br 24.02.

20 N.M.R. spectrum:

1'= 9.17 (doublet) 3H 1- 9.09 (singlet) 3H 1= 8.30-8.85 9H 25 r 6.7(singlet) 6H 1 6.32 (quartet) 2H 1 5.50 (multiplet) 1H EXAMPLE 6 r 9.18(doublet) 3H 1 9.10 (singlet) 3H 'r 8.97 (triplet) 3H 1 8.28 8.77 8H 16.73 (doublet) 6H 1 6.23 6.65 2H 1' 5.43 (multiplet) 1H r= 3.75-4.72 3HEXAMPLE 7 a. A solution of [1-methyl-3-(2,6,6-trimethyl-2-cyclohexenyl)-2(trans)-propenyl]dimethylamine (5.0 g) andl-propylbromide (6.0 g) in absolute methanol (10 cc) was refluxed for 3hours, and the solvent of the reaction mixture was distilled off underreduced pressure. To the residue was added a solution of potassiumiodide (5.7 g) in a mixed solvent of water and a small amount ofethanol, and the mixture was allowed to stand for 30 minutes. Themixture was concentrated to dryness under reduced pressure, and theresidue was dissolved in chloroform. After the filtration of thechloroform layer, the solvent of the filtrate was distilled off, and theresidue was recrystallized from a mixed solvent of benzene and ether togive colorless crystals (6.05 g) of[l-methyl-3-(2,6,6-trimeIhyl-Z-cyclohexenyl)-2(trans)-propenyl]-dimethylpropylammonium iodide.

N.M.R. spectrum:

-r= 9.l (doublet) 3H -r= 9.10 (singlet) 3H 1- 8.97 (triplet) 3H 'r=8.288.78 8H 7 6.75 (singlet) 6H 1- 6.30 6.67 2H 1' 5.43 (multiplet) 1H 13.70 4.70 3H b. With a solution of l-methyl-3-(2,6,6-trimethyl-2-cyclohexenyl)-2(trans)-propenyl]dimethylpropylammonium iodide (1.0 g)and silver chloride 1.0 g) in absolute methanol cc), colorless crystals(0.4 g) of [l-methyl-3-(2,6,6-trimethyl-2-cyclohexenyl)-2(trans)-propenyl]dimethylpropylammonium chloride were obtainedaccording to a similar manner to the Example 1 (b).

N.M.R. spectrum:

1 918 (doublet) 3H 1=9.ll (singlet) 3H 1= 8.98 (triplet) 3H 1 8.29 8.808H 1= 6.73 (doublet) 6H 7' 6.27 6.65 2H T=5.l25.8l lH 1'= 3.78 4.73 3HEXAMPLE 8 A solution of ll-methyl-3-(2,6,6-trimethyl-2-cyclohexenyl)-2(trans)-propenyl]dimethylamine (3.0 g) andl-heptylbromide (3.0 g) in methanol (30 cc) was refluxed for 3 hours,and thereto was added water (100 cc). The mixture was washed with ether,and thereto was added potassium iodide (10.0 g). The reaction mixturewas allowed to stand for 30 minutes, and then extracted with chloroform.The chloroform layer was washed with a saturated aqueous solution ofsodium thiosulfate and dried over sodium sulfate. The solvent wasdistilled off to give an oil (4.8 g) of[lmethyl-3-(2,6,6-trimethyl-Z-cyclohexenyl)-2(trans)-propcnylldimethylhcptylammonium iodide.

It was observed in the IR. spectrum of this oil that the absorptions at2750 and 2800 cm-1 based on the tertiary amine. which are existing inthat of l-methyl- 3-(2,6,6-trimethyl-2-cyclohexenyl)-2(trans)-propenyl]dimethylamine. have disappeared.

U.V. spectrum: (EtOH) EXAMPLE 9 A solution ofll-methyl-3-(2,6,6-trimethyl-2-cyclohexcnyl)-2(trans)-propenyl]dimethylamine (3.0 g) and l-octylbromide(3.0 g) in methanol (50 cc) was refluxed for 3 hours. and water wasadded thereto. The mixture was washed with ether and thereto was addedpotassium iodide (10.0 g). The reaction mixture was treated according toa similar manner to the Example 8 to give an oil (5.0 g) ofl-methyl-3-(2,6,6-trimethyl-Z-cyclohexenyl)-2(trans)-propenylldimethyloctylammonium iodide.

It was observed in the LR. spectrum of this oil that the absorptions at2750 and 2800 cm-1 based on the tertiary amine, which were existing inthat of [lmethyl-3-(2.6.6-trimethyl-Z-cyclohexenyl)-2(trans)-propenylldimethylamine. have disappeared.

U.V. spectrum: (EtOH) EXAMPLE 10 To a solution of[3-methyl-5-2,6,6-trimethyl-lcyclohexenyl)-2-(trans),4(trans)-pentadienylldimethylamine(1.3g) in small amount of absolute ethanol were added methyliodide(2.0g) and ether (50 cc) under cooling, and the reaction mixture wasallowed to stand. Precipitated crystals were gathered by filtration andrecrystallized from a mixed solvent of benzene and chloroform to givecrystals (0.6 g) of [3-methyl-5-(2.6,6-trimethyl-l-cyclohexenyl)-2(trans).4(trans)-pentadienyl]trimethylammonium iodide. m.p. 174 176C.

Analysis: C l-l NJ Calculated .l 32.59

Found .I 31.96.

EXAMPLE 1 l A solution of [l-methyl-3-(2,6,6-trimethyl-2-cyclohexenyl)-2(trans)-propenyl]dimethylamine (2.7 g) and1,2-ethyldibromide (2.0 g) in ethanol (30 cc) was refluxed for 3 hours,and the solvent of the reaction mixture was distilled off under reducedpressure. To the residue was added water cc), and the aqueous solutionwas washed with ether, and then thereto was added potassium iodide l0.0g). The reaction mixture was allowed to stand for 30 minutes, andextracted with chloroform. The chloroform layer was dried and thechloroform was distilled off. The residue was recrystallized fromethanol to give colorless crystals (1.8 g) of[l-methyl-3-(2,6,6-trimethyl-2-cyclohexenyl)-2(trans)-propenyl]dimethyl-(2-bromoethyl)ammonium iodide.

lt was observed in the IR. spectrum of this oil that the absorptions at2750 and 2800 cm-l based on the tertiary amine, which were existing inthat of [lmethyl-3-(2,6,6-trimethyl-2-cyclohexenyl)-2(trans)-propenylldimethylamine, have disappeared.

EXAMPLE 12 With a solution of [l-methyl-3-(2.6.6-trimethyl-2-cyclohexenyl)-2(trans)-propenyl]dimethylamine (2.3 g).1,3-propyldibromide (2.0 g) and potassium iodide (10.0 g) in ethanol (50cc), yellowish oil (3.2 g) oflmethyl-3-(2,6,6-trimethyl-2-cyclohexenyl)-2(trans)-propenyl]-dimethyl(3-bromopropyl)ammonium iodide was obtained accordingto a similar manner to the Example ll.

lt was observed in the LR. spectrum of this oil that the absorptions at2750 and 2800 cm-1 based on the tertiary amine, which were existing inthat of [lmethyl-3-(2,6,6-trimethyl-2-cyclohexenyl)-2(trans)-propenyH-dimethylamine, have disappeared.

EXAMPLE 13 With a solution of ll-methyl-3-(2,6,6-trimethyl-2-cyclohexenyl)-2(trans)-propenyl]dimethylamine (2.0 g),3-propargylbromide (1.1 g) and potassium iodide (10.0 g) in methanol (30cc), a yellowish oil (3.2 g) of1-methyl-3-(2,6,6-trimethyl-Z-cyclohexenyl)-2(trans)-propenyl]-dimethylpropargylammonium iodide was obtainedaccording to a similar manner to the Example 8.

LR. spectrum:

It was observed in the IR. spectrum of this oil that the absorptions at2750 and 2800 cm-1 based on the tertiary amine, which were existing inthat of [lmethyl-3-(2,6,6-trimethyl-Z-cyclohexenyl)-2(trans)-propenylldimethylamine, have disappeared.

EXAMPLE 14 A solution of [1-methyl-3-(2,6,6-trimethylcyclohexyl)propyl]dimethylamine (1.6 g) and a,3,4- trichlorotoluene (1.6 g) inabsolute methanol cc) was refluxed for 3 hours, and the solvent of thereaction mixture was distilled off. The residue was dissolved in a mixedsolvent of water 100 cc) and a small amount of ethanol; and potassiumiodide (4.0 g) was added thereto. Thirty minutes thereafter, thereaction mixture was concentrated to dryness under reduced pressure, andthe residue was dissolved in chloroform. After the filtration of thechloroform layer, the solvent of the filtrate was distilled off, and theresidue was recrystallized from a mixed solvent of benzene and ether togive colorless crystals (2.7 g) of [l-methyl-3-(2,6,6-trimethylcyclohexyl )-propyl]dimethyl( 3 ,4- dichlorobenzyl)ammoniumiodide, m.p. 193 195C.

Analysis: C l-l NCl l Calculated C 51.57, H 7.08, N 2.73, Cl 13.84, J24.77

Found C 51.84, H 6.95, N 2.85, Cl 13.62, .I 24.69.

EXAMPLE 15 A solution of [3-(2,6,6-trimethyl-l-cyclohexenyl)-2(trans)-propenyl]dimethylamine (2.0 g) in dry ether cc) was added tomethyliodide (2.0 g), and the reaction mixture was allowed to stand overnight. Precipitated crystals were gathered by filtration, andrecrystallized from a mixed solvent of ethanol, benzene and ether togive colorless crystals (2.3 g) of [3-(2,6,6-trimethyl-l-cyclohexenyl)-2(trans)-propenyl]trimethylammonium iodide,m.p. 180C.

EXAMPLE 16 With a solution of [l-methyl-3-(2,6,6-trimethylcyclohexyl)propyl]dimethylamine (1.6 g), a,2,4-trichlorotoluene1.6 g), and potassium iodide (4.0 g) in absolute methanol (10 cc),colorless crystals (2.4 g) of [1-methyl-3-(2,6,6-trimethyl cyclohexyl)propyl]dimethyl(2,4-dichlorobenzyl)ammonium iodide were obtainedaccording to a similar manner to the Example 14.

N.M.R. spectrum:

1' 8.38 (doublet) 3H 'r 6.86 (singlet) 3H 1 6.81 (singlet) 3H 1' 5.84(multiplet) 1H 1 5.06 (singlet) 2H r= 2.58 1= 2.58 (doublet) 1H 1 1.80(doublet) 1H 1' 2.51 (doublet) 1H EXAMPLE 17 a. A solution of[1-methyl-3-(2,6,6-trimethyl-2-cyclohexenyl)-2(trans)-propenyl]dimethylamine (3.0 g) anda,3,4-trichlorotoluene (4.0-g) in methanol (15 cc) was refluxed for 2hours, and thereto were added ethanol (40 cc) and then an aqueoussolution of potassium iodide (3.0 g). The solvent of the reactionmixture was distilled off under reduced pressure, and the residue wasrecrystallized from a mixed solvent of methanol and ether to givecolorless crystals (4.0 g) of[lmethyl-3-(2,6,6-trimethyl-2-cyclohexenyl)-2(trans)-propenyl]dimethyl(3,4-dichlorobenzyl)ammonium iodide, m.p. C.

Analysis: C H NCl J Calculated C 51.98, H 6.35, N 2.76, J 24.97

Found C 51.70, H 6.35, N 2.76, J 25.19.

b. A mixture of [l-methyl-3-(2,6,6-trimethyl-2-cyclohexenyl)-2(trans)-propenyl]dimethyl(3,4- dichlorobenzyl)ammoniumiodide (1.5 g), silver bromide (3.5 g) and sodium hydroxide (10 cc) wasrefluxed for 4 hours, and after the filtration of the reaction mixture,the solvent of the filtrate was distilled off. The residue was added toa mixed solvent of ether, methanol and benzene, and precipitatedcrystals were gathered by filtration to give humid colorless crystals(1.0 g) of [1-methy1-3-(2,6,6-trimethyl-2- cyclohexenyl-)-2(trans)-propenyl]dimethyl-( 3 ,4- dichlorobenzyl)ammonium bromide.

Analysis: C H NCl Br Calculated C 57.28, H 6.99, N 3.04, Br 1732 Found C57.18, H 7.00, N 3.26, Br 17.54.

EXAMPLE 18 A solution of [1-methyl-3-(2,6,6-trimethyl-2cyclohexenyl)-2(trans)-propenyl]dimethylamine (2.0 g) anda,3,4-trichlorotoluene (3.0 g) in methanol (10 cc) was refluxed for 2hours, and the solvent of the reaction mixture was distilled off underreduced pressure. The residue was recrystallized from a mixed solvent ofbenzene and ether to give hygroscopic colorless crystals (2.1 g) Y ofll-methyl-3-(2,6,6-trimethyl-2-cyclohexenyl)-2(trans)-propenyl]dimethyl( 3 ,4- dichlorobenzyl)ammoniumchloride.

Analysis: C22H NCl I Calculated C 63.39, H 7.74, N 3.36, Cl 25.51 FoundC 63.47, H, 7.94, N 3.04, Cl 25.81.

EXAMPLE 19 A mixture of [1-methyl-3-(2,6,6-trimethyl-2-cyclohexenyl)-2(trans)-propenyl]dimethylamine (2.0 g),a,2,4-trichlorotoluene (3.0 g) and methanol 10 cc) was refluxed for 5hours, and the solvent of the reaction mixture was distilled off underreduced pressure. The residue was dissolved in a small amount of benzeneand thereto was added a large amount of ether. The precipitated oil wasgathered by decantation and dissolved in a small amount of benzene andthereto was further added a large amount of ether. The solvent wasdistilled off to give colorless oil (4.5 g) of [l-methyl-3-(2,6,6-trimethyl-Z-cyclohexenyl)-2(trans)-propenyl]-dimethyl(2,4-dichlorobenzyl)ammonium chloride.

It was observed in the IR. spectrum of this oil that the absorptions at2750 and 2800 cm-1 based on the tertiary amine, which were existing inthat of the starting material, have disappeared.

EXAMPLE 20 a. A mixture of [1-methyl-3-(2,6,6-trimethyl-2-cyclohexenyl)-2(trans)-propenyl]dimethylamine (3.0 g),a,2,4-trichlorotoluene (3.0 g) and absolute methanol (10 cc) wasrefluxed for 6 hours, and the solvent of the reaction mixture wasdistilled off under reduced pressure. The residue was dissolved inethanol (20 cc) and a solution of potassium iodide (3.0 g) in water (5cc) was added thereto; The reaction mixture was concentrated to dryness,and the residue was dissolved in chloroform. After the filtration of thechloroform layer, the solvent of the filtrate was distilled off underreduced pressure. The residue was recrystallized twice from a mixedsolvent of methanol and ether to give colorless crystals (5.2 g) of[l-methyl-3-(2,6,6-trimethyl-2-cyclohexenyl)-2(trans)-propenyl]dimethyl(2,4- dichlorobenzyl)ammoniumiodide mono-hydrate. Analysis: C22H32NJCl'H O Calculated C 50.20, H6.51, N 2.66

Found C 50.53, H 6.20, N 2.98.

b. A mixture of [1-methyl-3-(2,6,6-trimethyl-2-cyclohexenyl)-2(trans)-propenyl]dimethyl(2,4- dichlorobenzyl)ammoniumiodide (1.0 g), silver bromide (2.0 g) and methanol cc) was refluxed for3 hours, and after the filtration of the reaction mixture, the solventof the filtrate was distilled off under reduced pressure. The residuewas recrystallized from a mixed solvent of benzene and ether to givecolorless crystals (0.7 g) of [1-methyl-3-(2,6,6-trimethyl-2-cyclohexenyl)-2(trans)-propenyl]-dimethyl(2,4- dichlorobenzyl)ammoniumbromide, m.p. 153 154C.

- EXAMPLE 21 Analysis: C- H NCU Calculated C 11.23, H 13.72, N 5.96, Cl15.09, 1 54.00

Found :C 11.52, H 13.70, N 5.91, C1 14.80, .1 54.07.

b.- A mixture of [1-methyl-3-(2,6,6-trimethyl-2-cyclohexenyl)-2(trans)-propenyl]dimethyl(4- chlorobenzyl)-ammoniumiodide (2.0 g), silver chloride (1.0 g) and absolute methanol (50 cc)was refluxed for 2 hours, and the reaction mixture was filtered. Thesolvent of the filtrate was distilled off to give hygroscopic colorlesscrystals (0.9 g) of [1-methyl-3-(2,6,6-trimethyl-Z-cyclohexenyl)-2(trans)-propenyl]dimethyl(4-chlorobenzyl)ammonium ride.

N.M.R. spectrum:

chlo- 1' 2.41 (quartet) 4H 1' 3.75 4.70 3H 1 5.05 (singlet) 2H 1 6.90(singlet) 6H 1' 8.26 (doublet) 3H 1' 8.42 (singlet) 3H r 9.10 (singlet)3H 1 9.18 (singlet) 3H EXAMPLE 22 To a solution ofl-[l-methyl-3-(2,6,6-trimethyl-2-cyclohexenyl)-2(trans)-propenyl]piperidine (3.0 g) in a small amount ofabsolute methanol was added methyliodide (2.1 g) under cooling. and thereaction mixture was allowed to stand over night. The solvent of thereaction mixture was distilled off under reduced pressure, and theresidue was dissolved in dil. hydrochloric acid. The aqueous solutionwas washed with ether, and then adjusted to an alkalinity by addingsodium bicarbonate. The aqueous solution was extracted with chloroform,and the chloroform layer was washed with water. After drying thechloroform layer, the solvent was distilled off under reduced pressure.The residue was dissolved in methanol and thereto was added ether, andthen the mixture was allowed to stand under cooling. Precipitatedcrystals were gathered by filtration and recrystallized from a mixedsolvent of methanol and ether to give crystals (1.3 g) of 1-methyl-l-[l-methyl-3- (2,6,6-trimethyl-2-cyclohexenyl)-2(trans)-propenyl]piperidinium iodide, m.p. 156 158C. Analysis: C H NJ CalculatedC 56.57, H 8.50, N 3.47, J 31.46

Found C 56.71, H 8.80, N 3.74, .1 31.50.

EXAMPLE 23 With a mixture of 4-[1-methyl-3-(2,6,6-trimethyl-2-cyclohexenyl)-2(trans)-propenyl]morpholine (8.2 g) and methyliodide 13.5g), crystals (2.0 g) of 4-methyl- 4-[l-methyl-3-(2,6,6-trimethyl-2-cyclohexenyl)-2(trans)-propenyllmorpholinium iodide, m.p. l67-l74C, were obtainedaccording to a similar manner to the Example 22.

Analysis: C H NOJ Calculated C 53.33, H 7.96, N 3.46, .l 31.31 Found C53.44, H 8.22, N 3.34, .l 31.05.

EXAMPLE 24 To a mixture (2.4 g) of 1-[1-methyl-3-(2,6,6-trimethyl-1-cyclohexenyl)-2(trans)- propenyllpyrrolidine and 1-[l-methyl-3-(2,6,6- trimethyl-2-cyclohexenyl)-2(trans)-propenyl1pyrrolidine (2:1) was added methyliodide (10.0 g), and thereaction mixture was sealed and allowed to stand over night. After thecompletion of the reaction, water (50 cc) was added to the reactionmixture, and the mixture was washed with ether. The mixture wasextracted with chloroform, and the chloroform layer wad dried overmagnesium sulfate. The chloroform was distilled off to give an oil (2.8g) consisting of l-methyl-l-[l-methyl-3-(2,6,6-trimethyl-1-cyclohexenyl)-2(trans)-propenyll-pyrrolidinium iodide and1-methy1-1-[1-methyl-3-(2,6,6-trimethyl-2-cyclohexenyl(trans)-propenyl]pyrrolidinium iodide. Analysis: C H NJCalculated C 55.51, H, 8.29, N 3.59, .1 32.61

Found C 55.54, H 8.06, N 3.41, .l 32.06.

N.M.R. spectrum:

1' 9.00 (singlet) 'r 9.10 (singlet) 6H 1' 9.18 (singlet) r 8.40(singlet) 1' 8.50 (singlet) 6H 1' 8.45 (singlet) 1' 7.05 (singlet) 3H 1-6.25 (singlet) 4H 1' 7.22 (singlet) 4H r=3.75-4.45 2-3H EXAMPLE 25 a. Amixture (1.0 g) of 1-methyl-3-(2,6,6-trimethyl-1-cyc1ohexenyl)-2(trans)-propenyl]dimethylamine andl-methyl-3-(2,6,6-trimethyl-Z-cyclohexenyl)-2(trans)-propenyl]-dimethylamine was added to a solution of methyliodide(1.0 g) in methanol (10 cc), and the reaction mixture was allowed tostand over night. To the reaction mixture was added ether, andprecipitated crystals were gathered by filtration, and thenrecrystallized from benzene to give colorless crystals (1.5 g)consisting of[1-methyl-3-(2,6,6-trimethyl-lcyclohexenyl)-2(trans)-propenyl]trimethylam-moniumiodide and [l-methyl-3-( 2,6,6-trimethyl-2-cyclohexenyl)-2(trans)-propenyl]trimethylammonium iodide (1:1).

It was observed in the LR. spectrum of the crystals that the absorptionsat 2750 and 2800 cm-1 based on the tertiary amine, which were existingin that of the starting material, have disappeared.

Analysis: C, H ,,NJ

Calculated C 52.89, H 8.32, N 3.85 Found: C 52.79, H 8.41, N 3.84.

N.M.R. spectrum:

1 9.16 (Singlet) r 9.10 (singlet) 6H 1- 9.00 (singlet) r 8.44(multiplet) 6H 1' 6.63 (singlet) 9H 1 5.40 (multiplet) 1H 1 3.7 4.72 3Hb. a mixture (0.5 g) of [1-methyl-3-(2,6,6-

trimethyl-l-cyclohexeny1)-2(trans)-propenylltrimethylammonium iodide and[l-methyl-3-(2,6,6-trimethyl-2-cyclohexenyl)-2(trans-propenyl]trimethylammonium iodide(1:1) was added to a solution of silver chloride (1.0 g) in absolutemethanol (30 cc), and the mixture was refluxed for 5 hours. After thefiltration of the reaction mixture, the solvent of the filtrate wasdistilled off under reduced pressure to give hygroscopic colorlesscrystals (0.3 g) consisting of 1-methyl-3-(2,6,6-trimethyl-l-cyclohexenyl)-2(trans)-propenylltrlmethylammonium chloride and [l-methyl-3-(2,6.6-trimethyl-2-cyclohexenyl)- 2(trans)- propenylltrimethylammoniumchloride (1:1).

N.M.R. spectrum:

1 9.15 (singlet) T 32 9.10 (singlet) (1H 1' 9.011 (singlet) r 2 8.4-1(multiplct) 6H 1' 6.60 (singlet) 9H 1 5.40 (multiplet) 1H 1' 3.x 4.1403H EXAMPLE 26 A mixture (5.0 g) of l-methyl-3-(2,6,6-trimethyl-1-cyclohexenyl)-2(trans)-propenyl]dimethylamine and[l-methy1-3-(2,6,6-trimethyl-2-cyclohexenyl)2(trans)-propenyl]dimethylamine (1:1) was added to a solution ofa a,3,4-trichlorotoluene (3.0 g) in 99 percent ethanol (30 cc), and themixture was sealed. The sealed reaction mixture was heated for hours at100C, and then the reaction mixture was adjusted to acidity by addingdil. hydrochloric acid, and washed with ether. The reaction mixture wasfurther adjusted to alkalinity by adding dil. aqueous solution of sodiumhydroxide, and extracted with ether. The ether layer was concentrated todryness, and to the residue were added water (100 cc) and potassiumiodide (10.0 g). The mixture was extracted with chloroform, thechloroform layer was dried. The chloroform was distilled'off, and thenthe residue was allowed to stand for 3 days. Precipitated crystals wererecrystallized from methanol to give yellowish crystals (4.2 g)consisting of [1-methyl-3-( 2,6,6-trimethyl-1-cyclohexenyl)-2(trans)-propenyl]dimethyl(3,4-dichlorobenzyl)ammonium iodide and1-methy1-3-(2,6,6-trimethyl-2-cyclohexenyl)-2(trans)-propenyl]dimethyl(3,4- dichlorobenzyl) ammoniumiodide (1:1).

It was observed in the IR. spectrum of the crystals that the absorptionsat 2750 and 2800 cm-1 based on the tertiary amine, which were existingin that of the starting material, have disappeared.

Analysis: C H NClJ' O Calculated C 50.20, H 6.51, N 2.66

Found C 49.92, H 6.80, N 2.46. N.M.R. spectrum:

1- 9.21 (singlet) 3H 1 9.21 (singlet) 3H 1' 8.98 (singlet) r 8.42(singlet) 3H 1' 8.26 (doublet) 3H 1- 6.87 (singlet) 6H 1' 5.20(multiple!) 1H 1 4.84 (singlet) 2H 1 3.75 4.65

1 2.51 (doublet) 1H 1' 2.16 (doublet) 1H 1 2.00 (doublet) 1H EXAMPLE 27emid astifia 2. [t:ta l!x ;3-(2 fifitim y cyclohexenyl)-2*(trans)dimethylamine and ]1-methyl-3-(2,6,6-trimethyl-2-cyclohexenyl)-2(trans)- propenyl]dimethylamine was added to a solution of a, 2,4-trichlorotoluene (2.4 g)in 99 percent ethanol (30 cc), and the reaction mixture was sealed andheated at 100C for 10 hours. After adjusting the mixture to an acidityby adding dil. hydrochloric acid, the reaction mixture was washed withether, and alkalized. The mixture was extracted with ether, and thesolvent of the ether layer was distilled off. To the residue was addedwater 100 cc), and then potassium iodide (20.0 g) was further addedthereto. The aqueous solution was extracted with chloroform, thechloroform layer was washed with a saturated aqueous solution of sodiumthiosulfate, and dried. The chloroform was distilled off, and theresidue was recrystallized from methanol to give crystals (4.2 g)consisting of [1-methyl-3-(2,6,6-trimethyl-2-cyclohexenyl)-2(trans)-propenyl]-dimethy1(2,4-dichlorobenzyl)ammonium iodide and1-methyl-3-(2,6,6-trimethyl-1-cyclohexenyl)-2(trans)-propenyl]-dimethyl(2,4-dichlorobenzyl) ammonium iodide. I

It was observed in the IR. spectrum of the above crystals that theabsorptions at 2750 and 2800 cm-1 based on the tertiary amine, whichwere existing in that of the starting material, have disappeared.Analysis: C H NCIJ Calculated: C 51.98, H 6.35, N 2.76

Found C 52.11, H 6.62, N 2.71. N.M.R. spectrum:

7 9.12 (singlet) 3H 1' 9.09 (singlet) 3H 'r 8.95 (singlet) 1 8.40(multiplet) 3H 1' 8.25 (doublet) 3H -Continued 1' 6.89 (singlet) 3H 16.82 (singlet) 3H -r 6.55 (multiplet) r 5.00 (singlet) 2H 1' 3.55 4.65(multiplet) 3H 7 2.60 (doublet) lH T 2.48 (doublet) 1H 1 1.89 (doublet)1H EXAMPLE 28 A solution of [l-methyl-3-(2,6,6-trimethyl-2-cyclohexenyl)-2(trans)-propenyl]dimethylamine (2.0 g) and3-propenylbromide (1.5 g) in methanol (30 cc) was refluxed for 3 hours,and the solvent of the reaction mixture was distilled off. To theresidue was added water (50 cc), and the aqueous solution was washedwith ether and potassium iodide (1.0 g) was added thereto. The reactionmixture was allowed to stand for 1 hour and extracted with chloroform.The chloroform layer was dried and the chloroform was distilled off. Theresidue was dissolved in benzene, and thereto was added ether.Precipitated crystals were gathered by filtration and dried to giveyellowish crystals (3.5 g) of[l-methyl-3-(2,6,6-trimethyl-2-cyclohexenyl)-2(trans)-propenyl]-dimethyl(2-propenyl)ammonium iodide. Analysis: C H NJCalculated C 55.53, H 8.28, N 3.60

Found C 55.35, H 8.18, N 3.57.

EXAMPLE 26 A solution of [1-methyl-3-(2,6,6-trimethyl-2-cyclohexenyl)-2(trans)-propenyl]dimethylamine (2.0

g) and 2-chloroethanol (1.0 g)-in ethanol (50 cc) was refluxed for 8hours, and the solvent of the reaction mixture was distilled off. Theresidue was dissolved in water (50 cc), and the aqueous solution waswashed with ether. Thereto was added potassium iodide (1.0 g), and themixture was allowed to stand for 1 hour. The mixture was extracted withchloroform, and the chloroform layer was washed with a saturated aqueoussolution of sodium thiosulfate and dried. The solvent was distilled off,and the residue was recrystallized from benzene to give yellowishcrystals (2.7 g) of[lmethyl-3-(2,6,6-trimethyl-Z-cyclohexenyl)-2(trans)-propenylldimethyK2-hydroxyethyl)ammonium iodide.

Analysis: C H NOJ Calculated C 51.91, H 82 O, N 3.56 Found C 51.78, H8.38, N 3.53.

EXAMPLE 30 A solution of l-methyl-3-(2,6,6-trimethyl-2-cyclohexenyl)-2(trans)-propenyl]dimethylamine (2.0 g) and2-chloropropionic acid (0.5 g) in methanol g) in methanol (50 cc) wasrefluxed for 8 hours on a water-bath, and the solvent of the reactionmixture was distilled off. The residue was dissolved in water, and theaqueous solution was washed with ether. Potassium iodide (3 g) was addedthereto, and the mixture was extracted with chloroform. The chloroformof the extract was distilled off, and the residue was recrystallizedfrom a mixed solvent of benzene and methanol to give crystals (2.] g) of[l-methyl-3-(2,6,6-trimethyl-2- cyclohexenyl)-b2(trans)-propenyl]dimethyl(2- carboxyethyl)ammonium iodide.

Analysis: C H NO l Calculated C 51.31, H 7.66, N 3.32, J 30.12 Found C51.03, H 8.06, N 3.10, .l 30.70.

EXAMPLE 31 A solution of [l-methyl-3-(2,6,6-trimethyl-2-cyclohexenyl)-2(trans)-propenyl]dimethylamine (2.2 g) and allylchloroacetate (1.1 g) in ethanol (50 cc) was refluxed for 2 hours, andthe solvent of the reaction mixture was distilled off. The residue wasdissolved in water (100 cc), and potassium iodide (5.0 g) was addedthereto. The aqueous solution was extracted with chloroform, and thechloroform layer was dried. The chloroform was distilled off to give ayellowish oil (3.4 g) of [l-methyl-3-(2,6,6-trimethyl-2-cyclohexenyl)-2(trans)-propenyl]-dimehtyl(allkyloxycarbonylmetehyl)ammonium dide.

It was observed in the IR. spectrum of this oil that the absorptions at2750 and 2800 cm-1 based on the tertiary amine, which were existing inthat of the starting material, have disappeared.

EXAMPLE 32 A solution of [1-methyl-3-(2,6,6-trimethylcyclohexyl)propyl]dimethylamine (3.0 g) and propargylbromide(3.0 g) in methanol (20 cc) was refluxed for 1 hour, and thereto wasadded a solution of potassium iodide (4.5 g) in water (15 cc). Aftershaking the mixture, water (50 cc) was added thereto, and the aqueoussolution was extracted with chloroform, the chloroform layer was washedwith water, dried and concentrated to dryness. The residue wasrecrystallized from a mixed solvent of ethanol and ether to givecolorless crystals (4.5 g) of [l-methyl-3-(2,6,6-trimethylcyclohexyl)propylldimethylproparglylammonium iodide, m.p. l65167C.

EXAMPLE 33 A solution of [3-(2,6,6-trimethyl-l-cyclohexenyl)-2(trans)-propenyl]dimethylamine (2.0 g) and proparglybromide (2.0 g) inmethanol (20 cc) was refluxed for 1 hour, and concentrated. To theresidue was added water, and the aqueous solution was washed with etherand extracted with chloroform. The chloroform layer was dried andconcentrated to dryness to give an oil (2.9 g) of[3-(2,6,6-trimethyl-1-cyclohexeny1)-2(trans)-propenyl]-dimethylproparglyammonium bromide.

It was observed in the LR. spectrum of this oil that the absorptions at2750 and 2800 cm-1 based on the tertiary amine, which were existing inthat of the-starting material, have disappeared.

EXAMPLE 34 a. A solution of [l-methyl-3-(2,6,6-trimethyl-2-cyclohexenyl)-2(trans)-propenyl]dimethylamine (5.0 g) and1,2-ethyldibromide (50 g) in absolute methanol (2 cc) was heated at Cfor 8 hours, and the excess 1,2-ethyldibromide was distilled offcompletely azeotropically by adding benzene. The residue wasrecrystallized from a mixed solvent of acetonitrile and ether to givehumid crystals (5.9 g) of [l-methyl-3-(2,6,6-trimethyl-2-cyclohexenyl)-2(trans)-propenyl]dimethyl(2-bromethyl)-ammonium bromide.

N.M.R. spectrum:

r=9.10-9.l7 (multiplet) 6H 1- 8.37 8.47 (multiple!) 7H 1- 7.75 8.17(multiplet) 4H -r 6.60 (doublet) 6H 1- 5.98 (singlet) 4H r 4.28 4.70(multiplet) 3H b. A solution of [l-methyl-3-(2,6,6-trimethyl-2-cyclohexenyl)-2(trans)-propenyl]dimethyl(Z-bromoethyl)-ammonium bromide(l g) and potassium iodide (0.54 g) in a mixed solvent of ethanol cc)anad water (5 cc) was stirred for 30 minutes at room temperature, andthe reaction mixture was concentrated under reduced pressure. Theresidue was extracted with chloroform, and the solvent of the chloroformlayer was distilled off. To the residue was added benzene, and thebenzene layer was concentrated to dryness. The residue wasrecrystallized from a mixed solvent of acetonitrile and ether to giveorange crystals 1.0 g) of 1-methyl-3-(2,6,6-trimethyl-2-cyclohexenyl)-2(trans)-propenyl]dimethyl(2-bromoethyl)ammonium iodide,m.p. 149 151C.

EXAMPLE 35 EXAMPLE 36 With a mixture of [2-(3.3,5-trimethylcyclohexyl)-ethylldimethylamine (1.0 g), benzene (30 cc) and ethyliodide (4.0 g).colorless crystals (1.3 g) of [2-(3.3,S-trimethylcyclohexyl)ethyl]dimethylethylammonium iodide, m.p.' 200202C, were obtained according to a similar manner to the precedingExample 35.

Analysis: C H 32 NJ Calculated C 50.99, H 9.13, N 3.96. J 35.92 Found C51.26, H 9.08, N 3.91, J 35.68.

EXAMPLE 37 A mixture of 2-(3,3,5-trimethylcyclohexyl)ethyl]-dimethylamine (1.0 g), l-heptylchloride (5.0 g) and absolute ethanol wasrefluxed for 7 hours, and then the solvent of the reaction mixture wasdistilled off under reduced pressure. To the residue was added asolution of potassium iodide (4.0 g) in a mixed solvent of ethanol cc)and water 10 cc), and water was added to the mixture. The aqueoussolution was extracted with chloroform, and the chloroform layer waswashed with water, dried and the solvent was distilled off. The residuewas recrystallized from a mixed solvent of ethanol and ether to givecolorless crystal (1.2 g) of [2-(3,3,5-trimethylcyclohexyl)ethyl]-dimethylheptylammonium iodide. m.p. lll 1l2c.Analysis: C H NJ Calculated C 56.72, H 10.00. N 3.31, .l 29.97

Found (56.53, H 9.96. N 315,130.15.

EXAMPLE 38 i To a solution of[2-(3,3,5-trimethylcyclohexyl)ethyl]dimethylamine (1.0 g) in benzene (30cc) was added propargylbromide (5.0 g), and the reaction mixture wasallowed to stand over night. The solvent was distilled off, and asolution of potassium iodide (4.0 g) in a mixed solvent of ethanol 15cc) and water 10 cc) was added to the residue. Water (50 cc) was addedto the reaction mixture and the aqueous solution was extracted withchloroform. The chloroform layer was washed with water, dried and thesolvent was distilled off to give a yellowish oil (1.2 g) of [2-(3,3,5-trimethylcyclohexyl)ethylldimethylpropargylammonium iodide.

IR. spectrum:

2200 cm-1 (C=C) It was observed in the IR. spectrum of this oil that theabsorptions at 2750 and 2800 cm-1 based on the tertiary amine, whichwere existing in that of the starting material, have disappeared.

The composition of the invention may contain other ingredients, forexample, protective colloids such as gelatin, glue, casein, gums andpolyvinyl alcohol; sodium polyphosphates; cellulose ethers, stabiliserssuch as ethylene diamine tetraacetic acid; other herbicides orpesticides; and stickers, for example, non-volatile oils.

The composition of the invention can be used in any conventionally knownmanner. The most suitable method of use, however, should be selecteddepending on the object of use, the type of plants to be treated and theperiod of application. Illustrative methods of application of thecomposition are spraying or dusting of the composition to the surfacesof leaves or and leafstalks of plants, treatment of soil on which plantsgrow with the composition, spraying of the composition onto seeds,fruits, tubers, etc soaking of seeds, fruits, tubers, etc., into thecomposition.

The compositions of the invention may be formulated as wettable powders,dusts, granules, solution, emulsifiable concentrates, emulsions andpasters.

Solid preparations can be prepared with inert powders to the compound[1]. The preparations thus can be homogeneous powders that either can beused as such, diluted with inert solids to form dusts, or suspended in asuitable liquid medium for spray application. The powders usuallycomprise the active ingredient admixed with suitable amounts ofconditioning agents. Natural clays, either absorptive such asattapulgite or relatively non-absorptive such as china clays,diatomaceous earth, synthetic fine silica, calcium silicate and otherinert solid carriers can be used. The active ingredient usually makes upfrom about 1 to about percent by weight, preferably from about 1 toabout 50 percent by weight, of these powder preparations. For conversionof the powders to dusts, talc, pyrophyllite, volcanic ash and otherdense, lactose, sodium chloride, rapid-settling inert solids customarilyare used.

Liquid preparations including the active ingredient can be prepared byadmixing the same with a suitable liquid medium. The active ingredientcan be either in solution or in suspension in the liquid medium. Typicalof the liquid media commonly emloyed are water, kerosene, Stoddardsolvent. xylene. alcohols, alkylated naphthalene. glycols and ketonessuch as diiosbutylketone, cyclohexanone, etc. The active ingredientusually makes up from about 1 to about 80 percent by weight, preferablyfrom about 1 to about 50 percent by weight, of these liquidpreparations. Some of these preparations are designed to be used assuch, and others to be extended with large quantities of water.

Preparations in the form of wettable powders or liquids can also includeone or more surface active agents such as wetting, spreading, dispersingor emulsifying agent. Thus mixtures of the above liquids with the activeingredient can contain an emulsifying agent to make an emulsifiable oilpreparation. The surface active agents cause the compositions of theliquid or dry to disperse or emulsify easily in water to give aqueoussprays. The surface active agents employed can be'of the anionic,cationic and/or non-ionic type.

EXAMPLES FOR THE PREPARATION OF COMPOSlTlON Practical and preferredembodiments of the compositions are illustrated in the followingExamples wherein parts are by weight.

EXAMPLE 1 [3-Methyl-5-t2.6.6-trimethyl-l-eyelohexenyl)-2.4- )5 partspentadienylltrimethylammonium iodide Polyoxyethylenealkylallylether 5parts The above mixture is diluted with water to a desired concentrationwhen it is used.

EXAMPLE 2 ll-Melhyl-3-t 2.(iKi-ll'illlll1)l-2-C)CiOhCXt-Iflyll-Z- partspropenylltrimethylamnionium iodide Tween 20 (Trade name) I part Ethanol89 parts The above mixture is diluted with water to a desiredconcentration when it is used.

The above mixture is diluted with water to a desired concentration whenit is used.

EXAMPLE 4 ll-MethylJ-t1.6.(Hrimelhyl-lcyclohexenyl)-2- 20 partspropeuylIdimethyllZA-dichlorohemyl)aiumonium iodidePolyoxyethyleuealkylallylether l0 parts Toluene 70 parts The abovemixture is diluted with water to a desired concentration when it isused.

EXAMPLE 5 [l-MelhylJJ I.tLh-trimethylcyelohexyllpropylL 2 partstrimethylammonium iodide Tale )8 parts The above mixture is diluted withwater to a desired concentration when it is used.

EXAMPLE 6 ll-Melhyl-3-(2.o.o-trimelhyl-l-cyclohexenyh-Z- 10 partspropenyl [trimethylammoniuni iodide Water )0 parts The above mixture isdiluted with water to a desired concentration when it is used.

EXAMPLE 7 ll-Methyl-3-(2.6.h-trimethyll-eyelohexenyl)-2 l0 partspropenyl]trimethylammoniuni iodide Lactose or NaCl )0 parts The abovemixture is prepared into tablets.

We claim:

1. A method for inhibiting plant growth which comprises applying, as aneffective ingredient, at least one of a quaternary ammonium salt of theformula:

2. The method of claim 1 in which the effective ingredient is a compoundof the formula:

AN+-R wherein R,, R R R R and R are each lower alkyl, A is a loweralkenylene, and X is chloride, bromide or iodide.

3. The method of claim 1 in which the effective ingredient is a compoundof the formula:

wherein R R R3 R R and R are each lower alkyl, A is a lower alkylene,and X is chloride, bromide or iodide.

4. The method ofclaim I wherein the effective ingredient is a compoundolthe formula:

1 A --N R2 X- R F t 5 wherein R R R R R and R are each lower alkyl, A isa lower alkadienylene, and X is chloride, bromide or iodide.

5. The method of claim 1 in which the effective ingredient is a compoundof the formula:

R4 R R wherein R R R R R and R are each lower alkyl, A is a loweralkylene and X is chloride, bromide or io- 2; 7. The method ofclaim l inwhich the effective ingredient is a compound of the formula:

A N R X i 2 R R wherein R R R R R and R are each lower alkyl, A is alower alkadienylene, and X is chloride, bromide or iodide.

8. The method ofclaim l in which the effective ingredient is a compoundof the formula:

A '-'N R wherein R R R R R and R are each lower alkyl, A is a loweralkenylene. and X is chloride, bromide or iodide.

9. The method ofclaim l in which the effective ingredient is a compoundof the formula:

R R ft wherein R R R R R and R are each lower alkyl, A is a loweralkylene, and X is chloride, bromide or iodide.

10. The method of claim l in which the effective ingredient is acompound of the formula:

wherein R R R R R and R are each lower alkyl, A is a loweralkadienylene, and X is chloride, bromide or iodide.

11. The method of claim 1 in which the effective ingredient is acompound of the formula:

wherein R R R R R and R are each lower alkyl, A is a lower alkenylene,and X is chloride, bromide or iodide.

12. The method of claim 1 in which the effective ingredient is acompound of the formula:

4 A N R2 X 5 l wherein R,, R R R R and R, are each lower alkyl, A is alower alkylcne, and X is chloride, bromide, or iodide.

IS. The method of claim 1 in which the effective ingredient is acompound of the formula:

A -N* R2 5 l wherein R R R R R and R are each lower alkyl, A is loweralkadienylene, and X is chloride, bromide or iodide.

14. The method of claim 1 in which the effective ingredient is acompound of the formula:

R R5 a A N+ R2 X in which R and R are each methyl; R is methyl, ethyl,propyl, heptyl, octyl, Z-bromoethyl, 3-bromopropyl, propargyl,3,4-dichlorobenzyl, 2,4-dichlorobenzyl, p-

1. AMETHOD FOR INHIBITING PLANT GROWTH WHICH COMPRISES APPLYING, AS ANEFFECTIVE INGREDIENT, AT LEAST ONE OF A QUATERNARY AMMONIUM SALT OF THEFORMULA:
 2. The method of claim 1 in which the effective ingredient is acompound of the formula:
 3. The method of claim 1 in which the effectiveingredient is a compound of the formula:
 4. The method of claim 1wherein the effective ingredient is a compound of the formula:
 5. Themethod of claim 1 in which the effective ingredient is a compound of theformula:
 6. The method of claim 1 in which the effective ingredient is acompound of the formula:
 7. The method of claim 1 in which the effectiveingredient is a compound of the formula:
 8. The method of claim 1 inwhich the effective ingredient is a compound of the formula:
 9. Themethod of claim 1 in which the effective ingredient is a compound of theformula:
 10. The method of claim 1 in which the effective ingredient isa compound of the formula:
 11. The method of claim 1 in which theeffective ingredient is a compound of the formula:
 12. The method ofclaim 1 in which the effective ingredient is a compound of the formula:13. The method of claim 1 in which the effective ingredient is acompound of the formula:
 14. The method of claim 1 in which theeffective ingredient is a compound of the formula:
 15. The method ofclaim 1 in which the effective ingredient is a compound of the formula:16. The method of claim 1 in which the effective ingredient is acompound of the formula:
 17. The method of claim 1 in which theeffective ingredient is a compound of the formula:
 18. The method ofclaim 14 in which R1, R2, R3, R4, R5 and R6 are each methyl, A is1-methyl-prop-3-enylene and X is bromide, chloride, or iodide.
 19. Themethod of claim 14 in which R1R2, R4, R5 and R6 are each methyl, R3 isethyl, A is 1-methyl-prop-3-enylene, and X is bromide or iodide.
 20. Themethod of claim 14 in which R1, R2, R4, R5 and R6 are each methyl, R3 ispropyl, A is 1-methyl-prop-3-enylene, and X is iodide.
 21. The method ofclaim 14 in which R1, R2, R4, R5 and R6 are each methyl, R3 is heptyl, Ais 1 -methyl-prop-3-enylene, and X is iodide.
 22. The method of claim 14in which R1, R2, R4, R5 and R6 are each methyl, R3 is 2-bromoethyl, A is1-methyl-prop-3-enylene, and X is iodide.
 23. The method of claim 14 inwhich R1, R2, R4, R5 and R6 are each methyl, R3 is propargyl, A is1-methyl-prop-3-enylene, and X is iodide.
 24. The method of claim 14 inwhich R1, R2, R4, R5 and R6 are each methyl, R3 is 3,4-dichlorobenzyl, Ais 1 -methyl-prop-3-enylene, and X is bromide or iodide.
 25. The methodof claim 14 in which R1R2, R4, R5 and R6 are each methyl, R3 is2,4-dichlorobenzyl, A is 1-methyl-prop-3-enylene, and X is bromide. 26.The method of claim 14 in which R1, R2, R4, R5 and R6 are each methyl,R3 is p-chlorobenzyl, A is 1-methyl-prop-3-enylene, and X is chloride oriodide.
 27. The method of claim 14 in which R1, R2, R4, R5 and R6 areeach methyl, R3 is allyl, A is 1-methyl-prop-3-enylene, and X is iodide.28. The method of claim 14 in which R1, R2, R4, R5 and R6 are eachmethyl, R3 is 2-hydroxyethyl, A is 1-methyl-prop-3-enylene, and X isiodide.
 29. The method of claim 15 in which R1R2, R3, R4, R5 and R6 areeach methyl, A is prop-3-enylene, and X is iodide.
 30. The method ofclaim 15 in which R1, R2, R4, R5 and R6 are each methyl, R3 is3,4-dichlorobenzyl, A is 1-methyl-prop-3-enylene, and X is iodide. 31.The method of claim 15 in which R1, R2, R4, R5 and R6 are each methyl,R3 is 2,4-dichlorobenzyl, A is 1-methyl-prop-3-enylene, and X is iodide.32. The method of claim 15 in which R1, R2, R3, R4, R5 and R6 are eachmethyl, A is Alpha -methylpropylene, and X is iodide.
 33. The method ofclaim 15 in which R1, R2, R3, R4, R5 and R6 are each methyl, A is3-methyl-penta-2,4-dienylene, and X is iodide.
 34. The method of claim16 in which R1, R2, R3, R4, R5 and R6 are each methyl, A is Alpha-methylpropylene, and X is bromide, chloride or iodide.
 35. The methodof claim 16 in which R1, R2, R4, R5 and R6 are each methyl, R3 is3,4-dichlorobenzyl, A is Alpha -methylpropylene, and X is iodide. 36.The method of claim 16 in which R1, R2, R4, R5 and R6 are each methyl,R3 is 2,4-dichlorobenzyl, A is Alpha -methylpropylene, and X is iodide.37. The method of claim 16 in which R1, R2, R4, R5 and R6 are eachmethyl, R3 is propargyl, A is Alpha -methylpropylene, and X is iodide.38. The method of claim 17 in which R1R2, R3, R4, R5 and R6 are eachmethyl, A is ethylene, and X is iodide.
 39. The method of claim 17 inwhich R1, R2, R4, R5 and R6 are each methyl; R3 is ethyl; A is ethyleneand X is iodide.
 40. The method of claim 17 in which R1, R2, R4, R5 andR6 are each methyl; R3 is heptyl; A is ethylene; and X is iodide. 41.The method of claim 17 in which R1, R2, R4, R5 and R6 are each methyl;R3 is propargyl; A is ethylene and X is iodIde.